Epoxidation of the products of codimerization of cyclopentadiene and cyclohexadiene hydrocarbons catalyzed by lanthanide-molybdenum polyoxometalates

Article abstract of DOI:10.1134/S1070363215050035

[4+2]-Codimerization of cyclohexa-1,3-diene, cyclopentadiene, and their methyl-substituted derivatives in the presence of H-forms of synthetic mordenite and natural clinoptilolite was studied. Application of zeolites as catalyst decreases the rate of di- and trimerization of cyclopentadiene and its methyl-substituted derivatives, increases the reaction selectivity with respect to their codimers with cyclohexa-1,3-diene and its methylsubstituted derivatives as well as 4-vinylcyclohexene. Epoxidation of the synthesized codimers with the adduct of hydrogen peroxide with urea in the presence of gadolinium- and neodymium-containing phosphorus molybdenum complexes as catalysts has been investigated, and optimal conditions for preparation of diepoxides of tricyclic dienes have been found.

Full text of DOI:10.1134/S1070363215050035

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 5, pp. 1025–1033. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © N.I. Garibov, Kh.M. Alimardanov, N.R. Dadashova, O.A. Sadygov, M.B. Almardanova, A.D. Kuliev, 2015, published in Zhurnal
Obshchei Khimii, 2015, Vol. 85, No. 5, pp. 726–734.
Epoxidation of the Products of Codimerization
of Cyclopentadiene and Cyclohexadiene Hydrocarbons Catalyzed
by Lanthanide–Molybdenum Polyoxometalates
N. I. Garibov, Kh. M. Alimardanov, N. R. Dadashova,
O. A. Sadygov, M. B. Almardanova, and A. D. Kuliev
Mamedaliev Institute of Petrochemical Processes, Azerbaijan National Academy of Sciences,
pr. Khojaly 30, Baku, AZ1025 Azerbaijan
e-mail: omar.sadiqov@gmail.com
Received November 20, 2014
Abstract—[4+2]-Codimerization of cyclohexa-1,3-diene, cyclopentadiene, and their methyl-substituted derivatives
in the presence of Н-forms of synthetic mordenite and natural clinoptilolite was studied. Application of zeolites
as catalyst decreases the rate of di- and trimerization of cyclopentadiene and its methyl-substituted derivatives,
increases the reaction selectivity with respect to their codimers with cyclohexa-1,3-diene and its methyl-
substituted derivatives as well as 4-vinylcyclohexene. Epoxidation of the synthesized codimers with the adduct
of hydrogen peroxide with urea in the presence of gadolinium- and neodymium-containing phosphorus
molybdenum complexes as catalysts has been investigated, and optimal conditions for preparation of
diepoxides of tricyclic dienes have been found.
Keywords: cyclopentadiene, cyclohexa-1,3-diene, 4-vinylcyclohexene, mordenite, clinoptilolite, acidic form,
dimerization, epoxidation, lanthanide-molybdenum polyoxometalate
DOI: 10.1134/S1070363215050035
6
The recently emerged interest to cyclopentadiene
and cyclohexadiene hydrocarbons is due to the
possibility of preparation of polyfunctional bridged
compounds, structural analogs of some natural terpene
compounds. Due to the increased raw-material
precursors of С –С cyclic unsaturated hydrocarbons
(Ar = p-BrC H ) system yields a mixture of exo/endo
4
isomers of methyl- and phenyl-substituted camphenes
[4]. Dimerization of cyclohexa-1,3-diene or its codi-
merization with hexadiene-2,4 in the presence of the
same catalytic system in CH Cl solution at 0°С leads
to tricyclo[6.2.2.0 ]dodeca-3.9-diene and 6-methyl-5-
propenylbicyclo[2.2.2]oct-2-ene in ≈70% yield and
endo:exo diastereoselectivity of 5 : 1 [4].
2
2
2
,7
5
6
[
1] and development of [4+2]-addition reactions, the
possibility has appeared to synthesize various adducts
2–4] that can act as monomers and intermediate
[
The Diels-Alder condensation of vinylboronates
with cyclopentadiene and cyclohexa-1,3-diene leading
to the boron derivatives of norbornene in up to quan-
titative yield and various ratio of the endo and exo
isomers has been described [5].
products for preparation of valuable drugs, perfume-
cosmetic goods, biologically active compounds, and
special polymers. In particular, condensation of
cyclohexa-1,3-diene-5-ol-6-one derivatives with cyclo-
2
.6
pentadiene into alkyl-substituted tricyclo[5,2,2,0 ]un-
deca-3,8-diene-10-ol-11-one has been reported [2].
Treatment of the adduct of cyclohexa-1,3-diene and
maleic anhydride with the solution containing NH OH
and NaClO yields endo-3-aminobicyclo[2.2.2]oct-5-
ene-2-endo-carboxylic acid [6].
Use of diphenyl- or tert-butylcyanoketenes in the
reaction with cyclohexa-1,3-diene as dienophile yields
ethers with bridged structure, isomerizing into bicyclo
4
3,8
3,8
[4.2.0 ]oct-4-en-1-one-2.2-diphenyl or bicyclo[4.2.0 ]-
In view of the above and aiming to synthesize a
wide range of polycyclic multifunctional compounds,
it was of interest to elaborate selective methods of
codimerization of cycloalkadiene hydrocarbons of
oct-4-en-1-one-2-cyano-2-tert-butyl [3].
Condensation of pentamethylcyclopentadiene with
·+
–
6
allene derivatives in the presence of the [Ar N + SbF ]
3
1
025

1
026
GARIBOV et al.
Scheme 1.
VI
II, cat., Δ
2
V
IV
VIII
2
,6
comparable reactivity and to study further functio-
nalization of the condensation products.
cyclopentadiene, endo-bicyclo[5.2.2.0 ]undeca-3,8-
diene VI was stable under the same conditions and
remained the major reaction product. No dimerization
Literature analysis has shown that polycyclic
unsaturated hydrocarbons oxidation followed by acid-
catalyzed transformation of epoxy- or hydroxy-
terpenoid structures is among the selective methods to
form new oxygen-containing compounds [7–10].
Selectivity of such transformations is determined by
the catalytic system efficiency and the reaction
conditions [11–14].
2,7
of cyclohexa-1,3-diene into tricyclo[6.2.2.0 ]dodeca-
,9-diene (VII) was observed. Thus, the selectivity of
co-condensation of cyclopentadiene with cyclohexa-
diene-1,3 in the presence of H-forms of the above
mentioned zeolites reached 90–92% with respect to
codimer VI (Scheme 1).
3
Structure of compound VI was elucidated using IR,
H, and C NMR spectroscopy as well as chromato-
mass spectrometry. Hydrogenation of the above-
mentioned mixture consisting mainly of diene VI
1
13
This work aimed to investigate condensation of
С –С cyclic dienes in the presence of H-forms of
5
8
natural clinoptilolite (Ai-Dag deposit, Azerbaijan) or
synthetic mordenite (SiO /Al O =10) and epoxidation
(
~98.5%) in the presence of Raney nickel at 100°С and
2
2
3
2,6
pressure of 10 MPa resulted in endo-bicyclo[5.2.2.0 ]-
undecane (IX) (its physico-chemical constants were
consistent with the reference data [15]). According to
the GC analysis, content of adduct VIII did not exceed
of the synthesized polycycloalkadiene hydrocarbons
with the adduct of hydrogen peroxide and urea
involving the in situ formed polyoxoperoxogadolinium
(
neodymium) phosphorus molybdenum complexes.
1
.0–1.5 wt %. That adduct was formed from cyclo-
Thermal condensation of methyl-substituted
pentadiene (a diene) and cyclohexa-1,3-diene (a
dienophile). Apparently, adduct VIII was unstable
under the reaction conditions due to higher strain in the
norbornene fragment in comparison with the bicyclo-
octane fragment in compound VI and, similarly to
dimer V, readily decomposed into monomers.
Therefore, under the studied conditions cyclohexa-
diene-1,3 acted majorly as a diene in the condensation
reaction, cyclopentadiene acting as a dienophile.
isomers of cyclopentadiene (I) with cyclohexa-1,3-
diene (II) as well as of the isomers of methylcyclo-
hexadiene-1,3 (III) with cyclopentadiene IV yielded a
complex mixture of dimers, codimers, and oligomers
of those hydrocarbons, the dimers being the major
components [15]. The ratio of dimers and codimers
varied in the range of (3–5) : 1. To determine the
activity of the H-form of natural clinoptilolite (or
synthetic mordenite), codimerization of cyclohexa-
diene-1,3 with cyclopentadiene was considered as a
model reaction.
Condensation of 4-vinylcyclohexene with cyclo-
pentadiene, cyclohexa-1,3-diene, and their methyl-
substituted derivatives proceeded majorly to form 5-
(cyclohexen-3-yl)bicyclo[2.2.1]hept-2-ene (Ха), 5-(cyclo-
hexe-3-yl)bicyclo[2.2.2]oct-2-ene (ХIa), and their
methyl-substituted derivatives Xb and XIb, respec-
tively, under the same conditions. In that case, vinyl
group of 4-vinylcyclohexene molecule acted as a
dienophile (Scheme 2).
It was found that dimerization of cyclopentadiene
was reversible under the reaction conditions (200–220°С
and 5 wt % of catalyst), and the rate of decomposition
2
,6
of the formed dimer, tricyclo[5.2.1.0 ]deca-3,8-diene
V), exceeded the rate of the monomer dimerization.
Unlike dimer V, codimer of cyclohexa-1,3-diene with
(
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015

EPOXIDATION OF THE PRODUCTS OF CODIMERIZATION
1027
Scheme 2.
R
R
Xa, Xb
R
R
XIa, XIb
R = H (a), CH
3
(b).
Scheme 3.
CH3
cat., Δ
+
CH3
_
XII XIV
XII, 3-Me; XIII, 4-Me; XIV, 5-Me.
Scheme 4.
CH3
H C
3
cat., Δ
+
IV
_
XV XVII
XV, 1-Me; XVI, 9-Me; XVII, 10-Me.
Reactions of cyclohexa-1,3-diene with the isomers
of methylcyclopentadiene or of cyclopentadiene with
methyl-substituted isomers of cyclohexa-1,3-diene occurred
similarly. In particular, codimerization of a mixture of
isomers of methylcyclopentadiene (48.7% of 1-methyl-
cyclopentadiene, 50.6% of 2-methylcyclopentadiene,
and 0.7% of 5-methylcyclopentadiene) with cyclo-
hexadiene-1,3 proceeded as shown in Scheme 3, while codi-
merization of the mixture of isomers of methylcyclo-
hexa-1,3-diene with cyclopentadiene followed Scheme 4.
adducts XII and XIII. Traces of adduct XIV were
formed, and 2-methyl-substituted isomers were not
1
3
detected. According to С NMR spectroscopy, methyl
groups in adducts XII and XIII were located in the
restricted cisoid position with respect to the bridge.
3
-Methylenecyclohex-1ene having rigid transoid
configuration did not react with cyclopentadiene
16, 17] (Scheme 4). Other isomers with the methyl
[
group in the cisoid position entered the reaction and
the products composition was consistent with the
isomeric composition of the original mixture of
methylcyclohexa-1,2-dienes. From the GC data, the
major products of the reaction were 1- and 9-methyl-
1
13
From the H and С NMR as well as GC analysis
data, the major products of reaction of methylcyclo-
pentadiene (48.7% 1-methylcyclopenta-1,3-diene, 50.6%
2
,6
2
-methylcyclopenta-1,3-diene, and 0.7% 5-methyl-
tricyclo[5.2.2.0 ]undeca-3,8-dienes. The reactivity of
isomers of methylcyclohexa-1,2-diene was much lower
cyclopenta-1,3-diene) with cyclohexa-1,3-diene were
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015

1
028
GARIBOV et al.
than that of unsubstituted diene II due to the methyl
substituent presence at the double bond. Under the
same conditions, the yield of codimer of dienes II and
IV was 1.5–1.8 times higher than that of codimers of
diene IV and the isomers of methylcyclohexa-1,3-diene.
A similar trend was observed in the case of codi-
merization of diene II with methylcyclopentadiene
compared to codimerization of dienes II and IV.
Epoxidation of compounds X–XVII was performed
via the two methods. In the first case, the reaction was
carried out in the presence of НСООН or СН СООН
3
at the substrate : oxidizer : RCOOH molar ratio of
1 : (1–2) : (0.2–0.4), at 60–70°С. Gadolinium(neody-
mium) phosphorus molybdenum complex GdPO ·H O·
4
2
(MoO )P Mo O
was used as catalyst, either
2
0.5
12 42
without support or supported on microstructured
carbon material. IR spectra of the unsupported and the
carbon-supported catalysts were substantially different.
The spectrum of the unsupported sample contained
strong absorption bands at 1020–1067 and 869–
We failed to find any physico-chemical, spectral, or
chromatographic parameters of isomeric methyltri-
cycloundeca-3,8-dienes XII–XVII in the literature. On
1
top of that, H NMR spectra of compounds VI–XXII
–
1
3–
4
9
62 cm , characteristic of the PO group and the Mo–
contained complex spin systems due to the presence of
bi-, tri-, and pentacyclic framework fragments in the
structure. Therefore, identification of various С –С
O–Mo + Mo=O bonds, respectively; the Gd–O bond
–
1
vibration gave rise to a strong band at 1461 cm and
1
0
12
–1
weaker bands at 400–720 cm . In the case of the
tricyclic dienes with cyclopentene, norbornene and
bicyclo-octene fragments was performed by comparing
3–
supported sample, intensity of the PO4 group
absorption band substantially decreased, whereas the
Mo–O–Мо and Mo=O bands grew stronger.
1
13
their GC, IR, H, and С NMR data with the reference
data of their partly or fully hydrogenated analogs.
Partial hydrogenation of codimers was carried out in a
flow system over nickel catalyst supported on
–
1
Additional absorption band at 1568 or 1617 cm
appeared, assigned to the С–О–Мo(Gd) bond.
–1
kieselguhr at 80–120°С and volume flow rate of 0.5 h .
Under those conditions, compounds XII–XVII were
hydrogenated mainly at the norbornene or bicyclo-
octene fragments.
ESR spectra of the catalyst contained the signals
with g = 2.094 and g = 1.941 [A (Мо) = 82 Gs and
||
┴
||
А (Мо) = 31 Gs] suggesting the presence of the
┴
3
+
МоО fragments in the complex. Investigation of ESR
signal intensity as function of the catalyst concentra-
tion in ethanol solution showed that the catalyst existed
predominantly in the dimeric state.
1
13
According to the data of IR, H, and С NMR
spectroscopy data, compounds XII–XVII were of the
endo configuration. The IR spectra contained
absorption bands of the –CR=C– (R = H, CH )
Adduct of hydrogen peroxide with urea was used as
oxidizer. The epoxidation proceeded via the in situ
formation mixture of Gd(III) or Nd(III)-containing poly-
oxoperoxomolybdate complexes (Scheme 5).
3
–
1
fragment at 3070–3035, 1578–1553, and 726–700 cm .
Unusual position of the ν(С=С) band was explained by
the strained double bond in the bicycloheptene or
bicyclooctene fragment of the molecule [18, 19]. The
ν(С–Н) absorption appearing as a doublet band at
In Scheme 5, the initially formed peroxyacid
participated in the formation of the active peroxo-
metalate complex, further taking part in addition of
electrophilic oxygen at the double bond of the tricyclic
unsaturated hydrocarbons. The epoxidation products
–
1
3
065–3050 and 3045–3030 cm , different from that
–
1
both in alkenes with terminal double bond (3080 cm )
and in cyclohexene (3027 cm ), was characteristic of
the discussed compounds.
–
1
1
13
structure was confirmed by IR, Н, and С NMR
1
13
H and C NMR spectra of the tricyclic dienes
spectroscopy as well as mass spectrometry.
1
were more informative. In the H NMR spectra, the
signals of protons at the double bond appeared as a
doublet at 5.58–5.62 ppm in the case of the five-
membered ring and at 5.64–6.23 ppm in the case of
bicycloheptene and bicyclooctene fragments. In the
The second epoxidation method consisted in the
reaction without any carboxylic acid. The initial
Gd(III) polyoxophosphorus molybdenum complex was
pretreated with 30% solution of Н О during 0.5 h at
2
2
4
0°С [12]. The so obtained peroxometalate complex
1
3
С NMR spectra, the signals at 131.4–133.3 ppm were
exhibited high activity in electrophilic addition of
oxygen atom at the double bond of the substrate.
assigned to the olefinic carbons of the five- and six-
membered rings, and those at 138.9–142.2 ppm
corresponded to the olefinic carbons of bicycloheptene
and bicyclooctene groups.
Reactivity of the studied codimers under conditions
of the induced epoxidation strongly depended on
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015

EPOXIDATION OF THE PRODUCTS OF CODIMERIZATION
1029
Scheme 5.
x
x
x
O
O
H O ,cat., Δ
O
2
2
O
y
y
y
_
H O , cat., Δ
XVIII XX
2
2
O
z
z
z
O
H O , cat., Δ
2
2
XXI, XXII
x = y = 1 (XVIII); x = 2, y = 1 (XIX); x = y = 2 (XX); z = 1 (XXI), 2 (XXII).
spatial orientation of the methyl group and hydrogen
atoms at the double bond. In particular, in the case of
trans-orientation of the methyl group and the hydrogen
atom at the double bond of the five-membered
fragment of the product of codimerization of dienes I
and II, attack of the double bond with active
electrophilic oxygen of the polyoxoperoxometalate
complex was hindered, and oxygen atom was majorly
added at the double bond of the bicyclooctene
fragment. On the contrary, epoxidation of the hardly
separable mixture of adducts of cocondensation of
methylcyclohexa-1,3-diene with diene IV, occurred at
the cyclopentene fragment due to the shielding of the
double bond of the bicyclooctene group. The highest
yield of epoxides (80–85%) was attained at 50–70°С
after 2–2.5 h. Further heating to 70–90°С and longer
reaction time caused the reaction of the oxirane ring
with unreacted molecules of the substrate to form the
cooligomerization products. The IR spectra of
oligomeric fractions contained typical absorption
–
1
bands of hydroxyl (3400–3640 cm ) and ethereal
–
1
(1075–1160 cm ) groups as well as of double bonds
–
1
(1620–1640 cm ).
Oligomers XXIII–XXV obtained, respectively, via
2,6
oxidation of tricyclo[5.2.1.0 ]deca-3,8-diene (V),
2
,6
tricyclo[5.2.2.0 ]undeca-3,8-diene (VI), tricyclo
2
,7
[
6.2.2.0 ]dodeca-3,9-diene (VII), and the product of
cooligomerization of XXIII with styrene (the XXIII :
styrene ratio of 1 : 4) XXVI were tested as film-
forming materials. Preliminary results have shown the
produced coatings can be used as thermoreactive film-
forming materials (see table).
Parameters of coatings obtained from oligomeric fractions of epoxidation of tricyclic diene hydrocarbons
Oligomer
Oligodivinylstyrene
varnish
Parameter
XXIII
dark-brown
4 h at 100°С
26
XXIV
dark-brown
3 h at 80°С
20
XXV
light-brown
3 h at 80°С
19
XXVI
light-brown
2 h at 80°С
19
color
light-brown
24 h at 20°С
20–30
Time of drying to grade “3”
Specific viscosity with В 3–4
at 20°С, s
Shock resistance, cm
50
50
50
≥50
50
Film elasticity in bending,
mm
Not more than 1 Not more than 1 Not more than 1 Not more than 1 Not more than 1
Adhesion by the method of
lattice cuts, score
Not more than 1 Not more than 1 Not more than 1 Not more than 1 Not more than 1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015

1
030
GARIBOV et al.
РО (0.113 g, 1.155 mmol) during 5–6 h. The product
4
EXPERIMENTAL
Н
3
was then cooled to room temperature, filtered off,
dried at 110–120°С, and heated at 220–250°С during
2–3 h; dark-yellow powder. The catalyst of the same
composition supported on highly dispersed carbon
material (AG-3) was prepared similarly. The catalyst
was added to the reaction mixture as a suspension in
acetic or formic acid.
IR spectra of suspensions in Vaseline oil or pellets
with KBr were recorded using an Alpha FTIR
–
1
spectrometer at 400–4000 cm or a Vertex (Bruker)
–
1
spectrometer at 100–700 cm . ESR spectra were
registered with a Bruker-BioSpin radiospectrometer at
2
5°С. Tuning to the internal field reference was
performed using ultradisperse diamond (g = 2.0036).
Peroxometalate complexes were prepared by
stirring of the above quantity of the catalytic system
with 30% aqueous Н О (3.14 g, 0.0923 mol) during
X-ray phase analysis was performed with a
Miniflex diffractometer (Rigaku) Analysis of inter-
layer distances calculated from the 2θ values showed
2
2
1
h at 40°С. The prepared complex was introduced
the presence of GdPO ·H O phase with d = 4.04;
4
2
into the system without any carboxylic acid.
2
2
.978; 2.79; 2.63; 2.057; 1.82 Å, corresponding to 2θ =
2
,6
endo-Tricyclo[5.2.2.0 ]undecadiene-3,8 (VI). A
2.3°; 29.8°, and 32.0° and (MoO )P Mo O phase
2
0.5
14 42
1
L autoclave was charged with 132 g of the dimer of
with d = 3.30; 6.325; 2.74; 2.50 Å [20, 21].
cyclopentadiene, 200 g of catalyzate prepared by
dehydration of cyclohexene oxidation product at 180°С
over γ-Al O promoted with 2% NaOH (cyclohexa-
Crystal structure of the prepared catalysts was
determined using an S–3400 N scanning electron
microscope equipped with an Oxford Instruments
Nano Analysis microanalysis system.
2
3
diene-1,3 content of 40 wt %) and 20 g of H-form of
ground clinoptilolite. The reaction mixture was stirred
during 3 h at 200°С. Cyclohexene and benzene
contained in the hydrocarbon mixture acted as solvent
during cocondensation. After the reaction, autoclave
was cooled with water, unreacted part of hydrocarbons
was distilled off at normal pressure, and the residue
was distilled in vacuum. Yield 103.4 g (70.8% with
respect to cyclohexa-1,3-diene), bp 71–73°С (13 mmHg),
GC analysis of composition and purity of the
starting reagents and epoxidation products was
performed using a Tsvet-500 chromatograph with a
flame-ionization detector (a 2000 × 3 mm column,
5
wt % of polyethylene glycol succinate on chromosorb
as a stationary phase, nitrogen as carrier gas, column
temperature 160°С, injector temperature 280°С). Chromato-
mass spectra were recorded using a GC 7890A-MSD
2
0
20
d
0.9878, n 5.5158, МR 44.8, calc. 45. IR spec-
4
D D
–
1
1
5975C Agilent Technologies instrument (column: HP5-
trum, ν, cm : 1611, 1649, 3020 [24]. Н NMR spec-
trum, δ, ppm: 6.28 d.d (1Н, Н , J9,8 = 9.9 Hz, J8,7 =
.5 Hz), 6.25 d.d (1Н, Н , J = 9.9 Hz, J9.1 = 6.5 Hz),
.24 d.d (1Н, Н , J = 9.9 Hz, J = 6.6 Hz), 5.59 m
1Н, Н ), 3.18 m (1Н, Н ), 2.59 m (1Н, Н ), 2.38 m
1Н, Н ), 2.28 m (1Н, Н ), 2.14 m (1Н, Н ), 1.76 m
1Н, Н ), 1.51 m (1Н, Н ) [26, 27]. C NMR
spectrum, δ , ppm: 37.9 (C ); 42.8 (C ); 133.7 (C );
8
MS, temperature program 40–280°C, helium as carrier gas).
9
6
6
(
(
(
9,8
Concentration of Н О was determined by redox
3
2
2
4
,3
3,2
titration with permanganate. Content of epoxide groups
was determined by thiosulfate method [22]. Cyclo-
hexadiene-1,3, a mixture of its methyl-substituted
derivatives [23], 4-vinylcyclohexene [24], and dimer
of cyclopentadiene isolated by vacuum distillation
from industrial fraction (99.0%, GC) were used as
starting hydrocarbons.
4
1
7
5у
2
5х
10х
10у
13
1
2
3
С
4
5
6
7
8
1
1
31.5 (C ); 38.7 (C ); 58.9 (C ); 39.8 (C ); 134.6 (C );
33.5 (C ); 30.9 (C ); 29.9 (C ) [16–18]. Mass
9
10
11
spectrum, m/z (relative intensity, %): 146 (4.4), 117
(4.3), 118 (6.9), 91 (11.4), 89 (2.7), 80 (100), 79
(59.6), 78 (9.9), 77(23.3), 68(13.7), 67(5.4), 66 (29.3),
Preparation of catalysts. Natural clinoptilolite
(
(
Ai-Dag deposit, Azerbaijan) or synthetic mordenite
SiO /Al O = 10) were used as catalysts for dimeriza-
11
65(19.0). Found, %: С 89.66, Н 10.13. C H14
.
2
2
3
tion after 4× treatment with 10% aqueous solution of
Calculated, %: C 90.40; H 9.59.
NH Cl, drying at 120°С during 2 h, and calcination at
4
2,7
Tricyclo[6.2.2.0 ]dodecadiene-3,9 (VII) was ob-
tained similarly from 200 g of the product of dehydra-
tion of cyclohexene oxidation product with diene II
content of 40%. Yield 63.4 g (79.2%) (exo : endo =
5
7
00–550°С during 4 h. Degree of decationization was
5 wt %.
Catalysts for epoxidation were prepared by reflux-
20
20
ing aqueous solutions of (NH) Mo O ·4H O (2.447 g,
17 : 83). bp 75–77°С (4 mmHg), d4 0.9963, nD
1.5245, MR 49.2, calc. 49.6. IR spectrum, ν, cm :
6
7
24
2
–
1
1
.98 mmol), Gd(NO ) ·5H O (0.5 g, 1.155 mmol) and
3
3
2
D
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015

EPOXIDATION OF THE PRODUCTS OF CODIMERIZATION
1031
1
12
13
14
1
(
610, 1650, 3020. Н NMR spectrum, δ, ppm: 5.91 d.d
126.9 (C ); 39.4 (C ); 38.8 (C ); for exo-isomer:
1
0
1
2
3
4
5
1Н, Н , J = 9.9 Hz, J10,1 = 6.6 Hz), 5.89 d.d (1Н,
Н , J1 = 9.9 Hz, J9,8 = 5.9 Hz), 5.89 d.d (1Н, Н ,
44.3 (C ); 135.9 (C ); 132.5 (C ); 49.4 (C ); 42.5 (C );
1
0,9
9
3
6
7
8
9
10
32.1 (C ); 28.1 (C ); 25.2 (C ); 45.6 (C ); 31.2 (C );
0,9
4
11
12
13
14
J3,4 = 9.9 Hz, J = 5.9 Hz), 5.60 m (1Н, Н ), 2.12–
127.5 (C ); 127.6 (C ); 39.4 (C ); 38.8 (C ). Found,
3,2
1
,2,8
5х
14
2
.16 m (3Н, Н ), 2.03 m (1Н, Н ), 1.75 m (1Н,
%: C 89.11; H 10.76. C H . Calculated, %: C 89.36; H
20
6
х
5у
7
Н ), 1.93 m (1Н, Н ), 1.51 m (1Н, Н ), 1.48 m (1Н,
Н ),1.58 m (2Н, Н
10.64.
,10-Dioxapentacyclo[6.3.1.0 .0 .0 ]dodecane
XVIII) was prepared similarly from 13.2 g (0.1 mol)
of dimer V. Yield 14.3 g (87% from GC), bp 50°С
7.5 mmHg), d 1.4956, nD 1.5206. IR spectrum, ν,
cm : 832, 858, 1250, 1260 (epoxide) 3010–3040. Н
NMR spectrum, δ, ppm: in tricyclooctane fragment:
.86 m (1Н, Н ), 2.85 m (1Н, Н ), 2.28 m (1Н, Н ),
.14 d (1Н, Н , J
.5 Hz), 1.76 m (1Н, Н ), 1.51 m (1Н, Н ), 1.42 m
1Н, Н ), 1.26 m (1Н, Н ); in bicycloheptane
fragment: 2.88 m (2Н, Н ), 1.72 m (1Н, Н ), 1.68 m
1Н, Н ), 1.54 m (1Н, Н ), 1.47 m (1Н, Н ), 1.40 m
1Н, Н ), 1.29 m (1Н, Н ). С NMR spectrum δ ,
ppm: 65.4 (С ), 62.6 (С ), 57.2 (С ), 48.9 (С ), 46.0
С ), 39.4 (С ), 33.6 (С ), 28.6 (С ), 21.2 (С ).
Found, %: С 73.10; Н 7.32. С Н О . Calculated, %:
С 73.15; Н 7.37.
6
у
11х,12х
11у,12у
13
), 1.33 m (2Н, Н
).
C
3,5 2,7 9,11
4
1
NMR spectrum, δ , ppm: for endo-isomer: 40.9 (C );
С
(
2
3
4
5
6
3
3
(
7.5 (C ); 133.3 (C ); 132.6 (C ); 27.9 (C ); 24.0 (C );
7
8
9
10
7.9 (C ); 39.7 (C ); 134.1 (C ); 128.2 (C ); 26.9
C ); 25.9 (C ). Found, %: C’, 89.72, H’, 10.24.
C H . Calculated, %: C 89.94, H 10.06.
20
4
20
(
1
1
12
–1
1
1
2
1
6
4
2
1
2
2
8
5
-(Cyclohexen-3-yl)bicyclo[2.2.1]hepten-2-ene (Ха)
was obtained similarly from 132 g (2 mol) of cyclo-
pentadiene and 108 g (1 mol) of 4-vinylcyclohexene-1.
37.5 g (79%) of Xа was obtained, bp 99–101°С
4 mmHg), d4 0.9768, nD 1.5158, MR 53.8, calc.
4.2. Н NMR spectrum, δ, ppm: in bicycloheptene
fragment: 6.28 d.d (1Н, Н , J = 11 Hz, J2,1 = 7.8 Hz),
.25 d.d (1Н, Н , J = 11 Hz, J = 7.8 Hz), 2.59 m
1Н, Н ), 2.29 m (1Н, Н ), 1.76 m (1Н, Н ), 1.62 m
1Н, Н ), 1.53 m (1Н, Н ), 1.51 m (1Н, Н ), 1.37 m
1Н, Н ); in cyclohexene fragment: 5.61 d.d (1Н, Н ,
J4 = 10.6 Hz, J4,5 = 6.7 Hz), 5.60 d.d (1Н, Н , J
0.6 Hz, J = 6.7 Hz), 2.06 m (1Н, Н ), 2.03 m (1Н,
Н ), 1.93 m (1Н, Н ), 1.80 m (1Н, Н ), 1.75 m (1Н,
Н ), 1.49 m (1Н, Н ). Mass spectrum, m/z (relative
intensity, %): 174 (8.5), 136 (2.3), 134 (4.7), 91 (5.8),
05 (1.6), 103 (1.8), 91 (6.8), 81 (10.7), 80 (100), 79
8s
8а
= 8.5 Hz), 1.89 d (1Н, Н , J
=
8s,8a
8s,8a
5
7х
6
7у
(
1
(
5
3
,5
6х
20
20
D
2
х
7х
6у
1
(
(
2
у
7у
13
2
С
3
,2
2
,4
7
9
6
3
6
3,2 3,4
1
5
10
11
12
4
1
7х
(
(
(
(
6
х
5
7у
10 12
2
6
у
4
3
3
,5 2,7 9,11
=
,3
3,4
4,10-Dioxapentacyclo[6.3.2.0 .0 .0 ]tridecane
(ХIХ) was prepared similarly from 14.6 g (0.1 mol) of
codimer VI. Yield 16.0 g (89.6% from GC), bp 102°С
7.5 mmHg), d 1.5016, n 1.5214, IR spectrum, ν,
cm : 835, 842, 860 (epoxide), 3050–3070. Н NMR
spectrum, δ, ppm: in tricyclononane fragment: 2.85 m
1Н, Н ), 2.86 m (1Н, Н ), 1.76 m (1Н, Н ), 1.74 m
(1Н, Н ), 1.52 m (2Н, Н ), 1.50 m (1Н, Н ), 1.42 m
1Н, Н ), 1.28 m (2Н, Н ) 1.26 m (1Н, Н ); in
bicycloheptane fragment: 2.88 m (2Н, Н ), 1.72 m
1Н, Н ), 1.68 m (1Н, Н ), 1.54 m (1Н, Н ), 1.47 m
2Н, Н ), 1.40 m (1Н, Н ), 1.29 m (1Н, Н ).
NMR spectrum δ , ppm: 62.9 (С ), 58.1 (С ), 48.9
(С ), 32.3 (С ), 30.1 (С ), 19.9 (С ). Found, %:
С 74.10; Н 7.87. С Н О . Calculated, %: С 74.13; Н
2
х
1
3,2
5
х
5у
2у
6
х
6у
2
0
20
(
4 D
–
1
1
1
(
1
2
4
1
50.6), 67 (1.5), 66 (21.8). Found, %: C 88.55; H
1.63. C H . Calculated, %: C 89.66; H 10.34.
18
(
1
3
5
8х,9х
7х,
6
8у,9у
7у,
(
5
-(Cyclohexen-3-yl)bicyclo[2.2.2]oct-2-ene (Хb)
3
,5
was prepared similarly from 200 g of the product of
dehydration of cyclohexene oxidation product diene II
content of 40% and 108 g (1 mol) of 4-vinylcyclo-
hexene-1. Yield 122.2 g (65%), bp 109–111°С (4 mmHg),
d4 0.9695, nD 1.5165, MRD 57.4, calc. 57.9. IR
spectrum, ν, cm : 1630–1635, 3010, 3045. Н NMR
spectrum, δ, ppm: in bicyclooctene fragment: 5.89 d.d
1Н, Н , J3 = 9.9 Hz, J2,1 = 6.7 Hz), 5.89 d.d (1Н, Н ,
J3,2 = 9.9 Hz, J = 6.7 Hz), 2.14 m (1Н, Н ), 2.12 m
1Н, Н ), 1.58 m (2Н, Н ), 1.53 m (1Н, Н ), 1.33 m
2Н, Н ), 1.28 m (1Н, Н ); in cyclohexene frag-
6
х
2х
7х
(
(
6
у
2у
7у
13
С
2
,4,7
9
С
6
10,12
11
12,13
20
20
–
1
1
1
1
14
2
7
.92.
2
3
3,5 2,8 10,12
(
4,11-Dioxapentacyclo[7.3.2.0 .0 .0
]tetra-
,2
1
decane (ХХ). A constant-temperature 100 mL glass
reactor equipped with thermometer, dropping funnel,
and condenser was charged with gadolinium
phosphorus molybdenum complex (0.05 mmol) and
treated with 30% solution of Н О (0.1–1.0 mmol)
during 0.5–1.0 h at 40–50°С. Then, 16.0 g of com-
pound VII (0.1 mol) and 30% solution of Н О in
dioxane (0.2–0.25 mol) were added dropwise, and the
mixture was stirred at 50–70°С during 2–4 h. Similar
experiments were also performed with urea peroxide in
3,4
4
7х,8х
6х
(
(
7
у,8у
6у
3
ment: 5.58 d.d (1Н, Н , J = 10.6 Hz, J3,2 = 6.7 Hz),
3,4
4
5
(
(
.58 d.d (1Н, Н , J = 10.6 Hz, J = 6.7 Hz), 2.06 m
4,3 4,5
2
2
2
х
5х
5у
1Н, Н ), 2.03 m (1Н, Н ), 1.93 m (1Н, Н ), 1.80 m
1Н, Н ), 1.75 m (1Н, Н ), 1.49 m (1Н, Н ).
2
у
6х
6у
13
C
2
2
1
NMR spectrum, δ , ppm: for endo-isomer: 44.4 (C );
С
2
3
4
5
6
1
2
36.9 (C ); 132.5 (C ); 49.8 (C ); 42.8 (C ); 32.1 (C );
7
8
9
10
11
8.7 (C ); 28.6 (C ); 45.9 (C ); 31.9 (C ); 127.2 (C );
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015

1
032
GARIBOV et al.
acetic acid. 16 g of compound ХХ was obtained. Yield
(Recycling of Liquid Pyrolysis Products), Moscow:
Khimiya, 1985.
2. Jeong, J.-P., Lee, O.-S., and Yang, K., Bull. Korean
Chem. Soc., 2002, vol. 23, no. 6, p. 829.
. Marton, А., Parvulescu, Н., Draghici, С., Varga, R.A.,
and Gheorgyhin, M.D., Tetrahedron, 2009, no. 65,
p. 7504. DOI: 10.1016/j.tet.2009.07.020.
. The Diels-Alder Reaction: Selected Practical Methods,
Fringuelli, F. and Taticchi, A., Eds., John Wiley &
Sons, 2002. DOI: 10.1002/0470845813.ch7.
20
8
2% (from GC), bp 118°С (7.5 mmHg), d 1.5028,
4
2
0
–1
nD 1.5235. IR spectrum, ν, cm : 850, 862, 3050–
3
Н
1
070. Н NMR spectrum, δ, ppm: 2.85–2.89 m (4Н,
3
,4,10,12
13
3
4
5
), 1.24–1.73 m (16Н, ring protons). С NMR
2
,4
8,9
6,12
spectrum, δ , ppm: 63.2 (С ), 58.1 (С ), 38 (С ),
С
7
,11
1,5
13,14
3
7
8
1.0 (С ), 29.8 (С ), 20.2 (С ). Found, %: С
4.93; Н 8.35. С Н О . Calculated, %: С 74.97; Н
1
2
16
2
.39.
-(4-Oxabicyclo[4.1.0]heptyl-3-exo-oxatricyclo-
6
. Sarotti, A.M., Pisano, P.L., and Pellegrinet, S.C., Org.
Biomol. Chem., 2010, no. 8, p. 5069. DOI: 10.1039/
c0ob00020e.
2
,4
[
1
3.2.1.0 ]octane (ХХI) was prepared similarly from
7.4 g (0.1 mol) of compound Ха, yield 16.5 g (80%
2
0
20
from GC), bp 138°С (8 mmHg), d 1.1084, n
1
NMR spectrum, δ, ppm: 2.88 m (1Н, Н ), 2.86 m
6. Palko, M., Sohar, P., and Fülöp, F., Molecules, 2011,
4
D
–
1
1
.5182. IR spectrum, ν, cm : 835, 858, 3010–3030. Н
no. 16, p. 7691. DOI: 10.3390/molecules16097691.
5
7. Alimardanov, Kh.M., Sadygov, О.А., Garibov, N.I., and
Abdullaeva, M.Ya., Russ. J. Org. Chem., 2012, vol. 48,
no. 10, p. 1302. DOI: 10.1134/S1070428012100077.
8. Kuznetsova, L.I., Kuznetsova, N.I., Lisitsyn, A.S.,
Bekk, I.E., Likholobov, V.А., and Ansel’, Zh.E., Kinet.
Catal., 2007, vol. 48, no. 1, p. 38. DOI: 10.1134/
S0023158407010065.
3
4
2
(
1Н,Н ), 2.85 m (1Н, Н ), 2.83 m (1Н, Н ), 1.22–1.74
1
3
m (18Н, ring protons). С NMR spectrum, δ , ppm:
6
3
fragment: 60.0 (С ), 57.8 (С ), 34.1 (С ), 33.1 (С ),
2
С
2
4
5
6
1
7.9 (С ), 65.7 (С ), 44.1 (С ), 39.6 (С ), 37.5 (С ),
1.9 (С ), 24.3 (С ); signals of the cyclohexane
7
8
5
'
3'
1'
2'
6
'
7'
8.0 (С ), 27.6 (С ). Found, %: С 75.66; Н 8.78.
9
. Carman, R.M. and Rayner, A.C., Austr. J. Chem., 1994,
vol. 47, no. 2, p. 195. DOI: 10.1071/CH9940195.
С Н О . Calculated, %: С 75.69; Н 8.80.
1
3
18
2
6
-(4-Oxabicyclo[4.1.0]heptyl-3-exo-4-oxatricyclo-
1
1
0. Salomatina, O.V., Yarovaya, O.I., and Barkhash, V.A.,
2
,4
[
1
1
4.2.1.0 ]nonane (ХXII) was prepared similarly from
8.8 g of compound XIa. Yield 19.2 g (78.5%), bp
46°С (5 mmHg), d 1.1068, n 1.5146. IR spectrum,
ν, cm : 850, 858, 862, 3010–3030. Н NMR spectrum,
δ, ppm: 2.86–2.88 m (4Н, Н ), 1.24–1.76 m (20Н,
ring protons). С NMR spectrum, δ , ppm: 65.4 (С ),
3.4 (С ), 39.6 (С ), 30.4 (С ), 28.8 (С ), 27.6 (С ),
2.4 (С ), 20.2 (С ); signals of the cyclohexane
Russ. J. Org. Chem., 2005, vol. 41, no. 2, p. 155 DOI:
1
0.1007/s11178-005-0141-y.
2
0
20
D
4
1. Kera, Y., Inagaki, A., Mochizuki, Y., Kominami, H.,
Yamaguchi, Sh., and Ichihara, J., J. Mol. Catal. A, 2002,
vol. 184, nos. 1–2, p. 413. DOI: 10.1016/S1381-1169
(02)00028-6.
–
1
1
2
–5
1
3
2
С
4
9
5
1
7
6
2
1
2. Timofeeva, M.N., Pai, Z.P., Tolstikov, A.G., Kustova, G.N.,
Selivanova, N.V., Berdnikova, P.V., Brylyakov, K.P.,
Shangina, A.B., and Utkin, V.A., Russ. Chem. Bull., 2003,
vol. 52, no. 2, p. 480. DOI: 10.1023/A:1023495824378.
8
9
5
'
3'
1'
2'
fragment: 60.0 (С ), 57.8 (С ), 34.1 (С ), 33.4 (С ),
8.0 (С ), 27.6 (С ). Found, %: С 76.28; Н 9.23.
6
'
7'
2
С Н О . Calculated, %: С 76.33; Н 9.15.
13. Modern Heterogeneous Oxidation Catalysis Design
Reactions and Characterization, Mizuno, N., Ed.,
Weinheim: Wiley-VCH Verlag, 2009.
1
4
20
2
Similarly, a hardly separable mixture of the isomers
of the corresponding diepoxides of 3-methyl- and 5-
2.7 3.5 9.11
14. Neumann, R., Inorg. Chem., 2010, vol. 49, no. 8,
methyl-3.8-dioxapentacyclo[6.3.2.0 .0 0 ]tridecane
and 1-methyl and 8-methyl-3.8-dioxapentacyclo
p. 3594. DOI: 10.1021/ic9015383.
2
.7 3.5 9.11
15. Aref’ev, О.А., Vorob’eva, N.S., Epishev, V.I., and
Petrov, Al.A., Neftekhim., 1972, vol. 12, no. 2, p. 171.
[
6.3.2.0 .0 .0 ]tridecane was obtained from the
mixture of the isomers of 3- and 4-methyltricyclo-
2
.6
16. Onishchenko, A.S., Dienovyi sintez (Diene Synthesis),
Мoscow: Akad. Nauk SSSR, 1963.
[
5.2.2.0 ]undecadiene-3.8 and 1- and 8-methyl-
2
.6
tricyclo[5.2.2.0 ]undecadiene-3.8. GC analysis of the
oxidation products of those dienes isomeric mixture
revealed the presence of four products differing in the
retention time beside the starting reagents [28].
1
7. Alimardanov, H.M., Sadygov, О.А., Babaev, R.S., and
Abdullaeva, M.Y., Process of Petrochem. and Oil
Refining, 2006, no. 2 (25), p. 17.
1
1
8. Zefirov, N.S. and Sokolov, V.I., Russ. Chem. Rev.,
1
967, vol. 36, no. 2, p. 87.
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. Berents, A.D., Vol-Einshtein, А.B., Mukhina, T.I., and
Avrekh, G.L., Pererabotka zhidkikh produktov piroliza
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015

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1033
2
2
2
2
0. Mirkin, L.I., Spravochnik po rentgenostrukturnomu
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2
2
2
2
5. Bellami, L.J., Infrared Spectra of Complex Molecules,
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1
977, USA.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015